The quantitative excited energy transfer reaction between cationic porphyrins on an anionic clay surface was successfully achieved. The efficiency reached up to ca. 100% owing to the "Size-Matching Rule" as described in the text. It was revealed that the important factors for the efficient energy transfer reaction are (i) suppression of the self-quenching between adjacent dyes, and (ii) suppression of the segregated adsorption structure of two kinds of dyes on the clay surface. By examining many different kinds of porphyrins, we found that tetrakis(1-methylpyridinium-3-yl) porphyrin (m-TMPyP) and tetrakis(1-methylpyridinium-4-yl) porphyrin (p-TMPyP) are the suitable porphyrins to accomplish a quantitative energy transfer reaction. These findings indicate that the clay/porphyrin complexes are promising and prospective candidates to be used for construction of an efficient artificial light-harvesting system.

The state-of-the-art of research on artificial photosynthesis is briefly reviewed. Insights into how Nature takes electrons from water, the photon-flux density of sunlight, the time scale for the arrival of the next photon (electron-hole) at the oxygen-evolving complex, how Nature solves the photon-flux-density problem, and how we can get through the bottleneck of water oxidation are discussed. An alternate route for a two-electron process induced by one-photon excitation is postulated for getting through the bottleneck of water oxidation.

We have been investigating complexes composed of nanolayered materials with anionic charges such as clay nanosheets and dye molecules such as cationic porphyrins. It was found that the structure of dye assembly on the layered materials can be effectively controlled by the use of electrostatic host-guest interaction. The intermolecular distance, the molecular orientation angle, the segregation/integration behavior, and the immobilization strength of the dyes can be controlled in the clay-dye complexes. The mechanism to control these structural factors has been discussed and was established as a size-matching effect. Unique photochemical reactions such as energy transfer through the use of this methodology have been examined. Almost 100% efficiency of the energy-transfer reaction was achieved in the clay-porphyrin complexes as a typical example for an artificial light-harvesting system. Control of the molecular orientation angle is found to be useful in regulating the energy-transfer efficiency and in preparing photofunctional materials exhibiting solvatochromic behavior. Through our study, clay minerals turned out to serve as protein-like media to control the molecular position, modify the properties of the molecule, and provide a unique environment for chemical reactions.

Photochemical CO2 reduction sensitized by rhenium–bipyridyl complexes has been studied through multiple approaches during the past several decades. However, a key reaction intermediate, the CO2-coordinated Re–bipyridyl complex, which should govern the activity of CO2 reduction in the photocatalytic cycle, has never been detected in a direct way. In this study on photoreduction of CO2 catalyzed by the 4,4′-dimethyl-2,2′-bipyridine (dmbpy) complex, [Re(dmbpy)(CO)3Cl] (1), we successfully detect the solvent-coordinated Re complex [Re(dmbpy)(CO)3DMF] (2) as the light-absorbing species to drive photoreduction of CO2. The key intermediate, the CO2-coordinated Re–bipyridyl complex, [Re(dmbpy)(CO)3(COOH)], is also successfully detected for the first time by means of cold-spray ionization spectrometry (CSI-MS). Mass spectra for a reaction mixture with isotopically labeled 13CO2 provide clear evidence for the incorporation of CO2 into the Re–bipyridyl complex. It is revealed that the starting chloride complex 1 was rapidly transformed into the DMF-coordinated Re complex 2 through the initial cycle of photoreduction of CO2. The observed induction period in the time profile of the CSI-MS signals can well explain the subsequent formation of the CO2-coordinated intermediate from the solvent-coordinated Re–bipyridyl complex. An FTIR study of the reaction mixture in dimethyl sulfoxide clearly shows the appearance of a signal at 1682 cm–1, which shifts to 1647 cm–1 for the 13CO2-labeled counterpart; this is assigned as the CO2-coordinated intermediate, ReII–COOH. Thus, a detailed understanding has now been obtained for the mechanism of the archetypical photochemical CO2 reduction sensitized by a Re–bipyridyl complex.

Intercalation of seven types of cationic surfactants, including polyfluorinated surfactants, into a cationexchangeable clay mineral, saponite, was investigated. All of the surfactants were found to intercalate in amounts exceeding the cation exchange capacity (CEC). This tendency was more evident in the cases of the polyfluorinated surfactants, ((((perfluoroalkanoyl)amino)ethyl)hexadecyl)dimethylammonium bromide (CnF-S, where n indicates the number of carbons in the perfluoroalkyl group, F denotes a fluorinated surfactant, and S denotes a surfactant having a single, long alkyl chain); C3F-S exhibited intercalation up to 4.4 times CEC as a saturated adsorption limit. The saponite interlayer distance increased upon surfactant intercalation and reached a constant value at intercalation levels exceeding CEC. The occupied areas for each surfactant molecule decreased in the order C1F-S > C2F-S > C3F-S among the polyfluorinated surfactants. All of the experimental results, including the saturated intercalation levels, the occupied areas, the interlayer distances, and the DSC measurements, suggest that CnF-S intercalated in saponite forms a rigidly packed bilayer structure in which the long alkyl chains tilt at an angle of ca. 35°with respect to the clay surface. The microscopic structure of the hybrid compounds is discussed.

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Solvent and substituent e †ects on the competition between internal conversion and triplet formation were studied systematically for aminoÑuorenones and their N-methylated derivatives. Intersystem crossing (ISC) was found to be the dominant process for the singlet excited 1-amino-and 1-methylaminoÑuorenone in all solvents. The short Ñuorescence decay time of these compounds does not originate from intramolecular hydrogen bonding induced internal conversion but it is due to the fast triplet formation. Rather slow s~1) and solvent insensitive intersystem crossing characterizes the photophysical behavior of (k ISC O 4.8 ] 107 2-, 3-and 4-aminoÑuorenones but their internal conversion rate strongly increases with solvent polarity. The change of the internal conversion rate constants with molecular structure and solvent can be rationalized in terms of the energy gap law.

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